Glass adhesive for repairing Yao-head black porcelain and preparation method thereof

Abstract

According to the glass adhesive for repairing Yao-head black porcelain and the preparation method of the glass adhesive, raw materials are poured into a nylon ball milling tank according to the components, and wet ball milling is carried out. After drying, screening out mixed powder with the required particle size; quickly pouring the mixed raw materials into a heated glass furnace, preserving heat, heating the glass furnace, and preserving heat to obtain a high-temperature molten substance; rapidly pouring the high-temperature molten substance into a liquid quenching medium, continuously stirring, quenching, cooling, and collecting cullet; and performing ultrasonic cleaning and drying on the cullet, and grinding to obtain glass powder. Manufacturing a colloid; the ballstone, the glass powder, the colloid and deionized water are poured into a nylon ball milling tank for ball milling, and the glass adhesive is obtained. The glass adhesive can play a certain positive role in repairing and bonding the Yao-head black porcelain.

Description

Technical Field

[0001] This invention relates to the field of ceramic material repair technology, and specifically to a glass adhesive for repairing Yaotou black porcelain and its preparation method. Background Technology

[0002] Shaanxi, as the world-renowned ancient capital of thirteen dynasties, embodies the essence of Chinese culture, and its historical artifacts naturally attract much attention. Ancient ceramics unearthed in Shaanxi, as carriers of Chinese civilization, have drawn numerous scholars to study them. Yaotou Town in Chengcheng County, Shaanxi Province, is home to Yaotou black porcelain, hailed as the "Black Pearl of the Orient," with a history dating back to the Tang Dynasty. It possesses significant historical, cultural, and artistic value. However, the drastically reduced number of Yaotou kilns and a lack of public awareness regarding cultural relic protection have led to the destruction of a large quantity of valuable Yaotou black porcelain, making restoration difficult. Summary of the Invention

[0003] To overcome the shortcomings of the existing technology, the purpose of this invention is to provide a glass adhesive for repairing Yaotou black porcelain and its preparation method. This glass adhesive can play a positive role in the repair and bonding of Yaotou black porcelain, providing a new approach for the efficient protection of cultural relics.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A glass adhesive for repairing Yaotou black porcelain, characterized in that it comprises the following components by weight percentage: 40%~55% quartz powder; 5%~21% calcined alumina; 0.5~16% B2O3; 0.5~20% CaO 4%~12% MgO; 1%~10% K2O; 1%~3% ZrO2; 0~16% Li2O; 0.2~1.6% TiO2; 0%~15% P2O5; 16% Na2CO3.

[0005] A method for preparing a glass adhesive for repairing Yaotou black porcelain, characterized by comprising the following steps: Step 1: According to the mass percentage, add 40%~55% quartz powder, 5%~21% calcined alumina, 0.5~16% B2O3, 0.5~20% CaO, 4%~12% MgO, 1%~10% K2O, 1%~3% ZrO2, 0~16% Li2O, 0.2~1.6% TiO2, and 0%~15% P2O5, and additionally add 16% Na2CO3. Pour the mixture into a nylon ball mill jar for wet ball milling, dry it, and then sieve it. The raw material for B2O3 is boric acid, the raw material for CaO is CaCO3, the raw material for K2O is K2CO3, the raw material for Li2O is Li2CO3, and the raw material for P2O5 is ammonium dihydrogen phosphate. Step 2: Transfer the mixed raw materials to a quartz crucible inside a glass furnace that has been preheated to 1000-1100℃. Hold the temperature for the first time, then raise the temperature of the glass furnace to 1450℃ at a heating rate of 2~3℃ / min, and hold the temperature again to fully melt the mixed powder and obtain high-temperature molten material A. Step 3: Quickly open the glass furnace, pour the high-temperature molten material A into the liquid quenching medium and stir constantly to prevent sticking and cool down quickly. Collect the irregular glass shards after cooling. Step 4: Ultrasonically clean and dry the collected irregular glass fragments, then transfer the glass fragments into a mortar and grind them into glass powder B. Step 5: PVA, anhydrous ethanol and deionized water are poured into a water bath and stirred until they are evenly mixed. The water bath is then heated to 90°C and kept at that temperature for 12 hours to obtain colloidal C. Step 6: Pour the ball stone, glass powder B, colloid C, and deionized water into a nylon ball mill jar and ball mill for 24 hours to obtain mixed colloid D, which is the glass adhesive.

[0006] In step 1, the liquid medium for wet ball milling can be distilled water or anhydrous ethanol, and the mass ratio of raw material, liquid medium and ball milling is 1:6:2.

[0007] The initial heat preservation time in step 2 is 10-15 minutes; the second heat preservation time is 40-55 minutes.

[0008] The liquid quenching medium in step 3 is distilled water at a temperature of 10~20℃.

[0009] In step 3, the irregular glass particles are collected using non-woven fabric.

[0010] Step 4 further includes: pouring the ground glass powder into a ball mill jar for wet ball milling, drying it, and then using a sieve to separate the glass powder of the required particle size.

[0011] The liquid medium for wet ball milling in step 4 is distilled water, and the mass ratio of raw material, distilled water and ball is 1:3:1, and the diameter of the ball is less than 3 mm.

[0012] The sieves used in steps 1 and 4 are both 200 mesh.

[0013] In step 5, during the heating and heat preservation stage, a water bath with magnetic stirring function must be used to stir the colloid, and the opening of the water bath must be sealed with plastic wrap to prevent excessive evaporation of moisture.

[0014] In step 6, the ratio of spherical particles, glass powder, colloid, and deionized water is 3:2:0.6:3. A glass adhesive for repairing Yaotou black porcelain is applied to the glass used in the repair of Yaotou black porcelain.

[0015] The present invention has the following beneficial technical effects: 1) This invention employs a relatively easy-to-operate glass preparation process, introducing multiple elements to obtain a multi-element glass system as an important component of the adhesive, which has a positive effect on repairing Yaotou black porcelain. The reasons are as follows: First, boric acid forms [BO3] triangles and [BO4] tetrahedra at high temperatures, and B³⁺ can penetrate into the Si-O-Si bond gaps on the Yaotou black porcelain cross-section, forming BO-Si covalent bonds, which helps enhance the strength of the adhesive itself. Second, the addition of calcined alumina can improve the stability of the glass network and enhance mechanical properties. Third, alkali metal carbonates (Na₂CO₃, K₂CO₃, Li₂CO₃), after melting at high temperatures, play a certain role in breaking up the glass network, improving the glass's fluidity and reducing its viscosity, which is beneficial for the glass adhesive to uniformly cover and fill the cracks in the Yaotou black porcelain. The lower viscosity melt after lowering the temperature also enhances its mechanical properties. Fourth, TiO₂ can both reduce the surface tension of the glass and improve the wettability of the adhesive to the glass, promoting non-uniform nucleation and shortening the curing time. Fifthly, ZrO2 can suppress glass phase separation and improve the mechanical properties of glass adhesives.

[0016] 2) During the high-temperature bonding process, the organic matter in the glass adhesive prepared by this invention volatilizes, leaving only inorganic matter—glass. This improves its resistance to damp heat and aging, and enhances its chemical stability, which is beneficial for the long-term preservation of cultural relics.

[0017] 3) The glass adhesive prepared by this invention will precipitate crystalline phase during the high-temperature bonding process. Through the synergistic optimization of crystalline phase and glass network, the crystalline phase and glass phase form an interlocking structure, which significantly improves the strength of the adhesive layer and plays a positive role in the repair of Yaotou black porcelain. Attached Figure Description

[0018] Figure 1 The XRD patterns of the multi-element glasses prepared in Examples 1 to 4 of this invention; Figure 2 The DSC spectra of the multi-element glasses prepared in Examples 3 and 4 of this invention are shown. Detailed Implementation

[0019] The present invention will be further described in detail below with reference to specific embodiments. These descriptions are for explanation purposes only and are not intended to limit the scope of the invention. Example

[0020] Step 1: According to the mass percentage, pour 47.2% quartz powder, 20.3% calcined alumina, 8.5% B2O3 (raw material: boric acid), 1% CaO (raw material: CaCO3), 11.5% MgO, 9.5% K2O (raw material: K2CO3), 1% ZrO2, 0% Li2O (raw material: Li2CO3), 1% TiO2, and 0% P2O5 (raw material: ammonium dihydrogen phosphate) into a nylon ball mill jar for wet ball milling. After weighing, add an additional 16% Na2CO3, dry, and then sieve using a 200-mesh sieve. Step 2: Transfer the mixed raw materials to a quartz crucible inside a glass furnace that has been preheated to 1000-1100℃. Hold the temperature for the first time, then raise the temperature of the glass furnace to 1450℃ at a heating rate of 2-3℃ / min. Hold the temperature again to fully melt the mixed powder and obtain high-temperature molten material A. Step 3: Quickly open the glass furnace and pour the high-temperature molten liquid into the liquid quenching medium while stirring constantly to prevent sticking and to cool it down rapidly. Collect irregularly shaped glass fragments; Step 4: Ultrasonically clean and dry the collected irregular glass fragments, then transfer the glass fragments into a mortar and grind them into glass powder B; then sieve them using a 200-mesh sieve. Example

[0021] Step 1: According to the mass percentage, pour 42% quartz powder, 17% calcined alumina, 1% B2O3 (raw material: boric acid), 20% CaO (raw material: CaCO3), 5% MgO, 3% K2O (raw material: K2CO3), 1% ZrO2, 0% Li2O (raw material: Li2CO3), 1% TiO2, and 10% P2O5 (raw material: ammonium dihydrogen phosphate) into a nylon ball mill jar for wet ball milling. After weighing, add an additional 16% Na2CO3, dry, and then sieve using a 200-mesh sieve. Step 2: Transfer the mixed raw materials to a quartz crucible inside a glass furnace that has been preheated to 1000-1100℃. Hold the temperature for the first time, then raise the temperature of the glass furnace to 1450℃ at a heating rate of 2-3℃ / min. Hold the temperature again to fully melt the mixed powder and obtain high-temperature molten material A. Step 3: Quickly open the glass furnace and pour the high-temperature molten liquid into the liquid quenching medium while stirring constantly to prevent sticking and to cool it down rapidly. Collect irregularly shaped glass fragments; Step 4: Ultrasonically clean and dry the collected irregular glass fragments, then transfer the glass fragments into a mortar and grind them into glass powder B; then sieve them using a 200-mesh sieve. Example

[0022] Step 1: According to the mass percentage, pour 54% quartz powder, 14% calcined alumina, 10% B2O3 (raw material: boric acid), 7% CaO (raw material: CaCO3), 5% MgO, 5% K2O (raw material: K2CO3), 1% ZrO2, 2% Li2O (raw material: Li2CO3), 1% TiO2, and 1% P2O5 (raw material: ammonium dihydrogen phosphate) into a nylon ball mill jar for wet ball milling. After weighing, add an additional 16% Na2CO3, dry, and then sieve using a 200-mesh sieve. Step 2: Transfer the mixed raw materials to a quartz crucible inside a glass furnace that has been preheated to 1000-1100℃. Hold the temperature for the first time, then raise the temperature of the glass furnace to 1450℃ at a heating rate of 2-3℃ / min. Hold the temperature again to fully melt the mixed powder and obtain high-temperature molten material A. Step 3: Quickly open the glass furnace and pour the high-temperature molten liquid into the liquid quenching medium while stirring constantly to prevent sticking and to cool it down rapidly. Collect irregularly shaped glass fragments; Step 4: Ultrasonically clean and dry the collected irregular glass fragments, then transfer the glass fragments into a mortar and grind them into glass powder B; then sieve them using a 200-mesh sieve. Example

[0023] Step 1: According to the mass percentage, pour 46% quartz powder, 9% calcined alumina, 10% B2O3 (raw material: boric acid), 7% CaO (raw material: CaCO3), 5% MgO, 2% K2O (raw material: K2CO3), 3% ZrO2, 15% Li2O (raw material: Li2CO3), 1% TiO2, and 2% P2O5 (raw material: ammonium dihydrogen phosphate) into a nylon ball mill jar for wet ball milling. After weighing, add an additional 16% Na2CO3, dry, and then sieve using a 200-mesh sieve. Step 2: Transfer the mixed raw materials to a quartz crucible inside a glass furnace that has been preheated to 1000-1100℃. Hold the temperature for the first time, then raise the temperature of the glass furnace to 1450℃ at a heating rate of 2-3℃ / min. Hold the temperature again to fully melt the mixed powder and obtain high-temperature molten material A. Step 3: Quickly open the glass furnace and pour the high-temperature molten liquid into the liquid quenching medium while stirring constantly to prevent sticking and to cool it down rapidly. Collect irregularly shaped glass fragments; Step 4: Ultrasonically clean and dry the collected irregular glass fragments, then transfer the glass fragments into a mortar and grind them into glass powder B; then sieve them using a 200-mesh sieve.

[0024] Figure 1 The XRD patterns of the multi-element glasses prepared in Examples 1 to 4 are shown. It can be seen that each sample exhibits representative amorphous characteristic peaks of glass, especially the broad, gently convex "bun peaks" at 25–40°, which do not correspond to definite crystal plane indices. This reflects the short-range ordered, long-range disordered structural characteristics of the glass, indicating that glass has been successfully prepared.

[0025] Figure 2 The DSC spectra of the multi-element glasses prepared in Examples 3 and 4 are shown. Figure a1) shows that the first heating in Example 3 resulted in three peaks, with the peak between 520 and 550 °C representing its glass transition temperature. This indicates that the glass has transitioned from a brittle glassy state to a soft, elastic state, representing a sudden change in physical properties. Subsequently, exothermic and endothermic peaks appeared at 934 °C and 1034.7 °C, respectively, indicating that crystallization occurred in the glass material. Figure a2) shows that the second heating in Example 3 only resulted in one peak at the glass transition temperature, with the endothermic and exothermic peaks disappearing. This indicates that the second heating did not induce structural reorganization, and the second temperature increase did not induce a new crystallization process.

[0026] As shown in Figure b1), the first heating in Example 4 produced four peaks, with the peak between 460 and 480°C representing its glass transition temperature. This indicates that the glass has transitioned from a brittle, hard glassy state to a soft, elastic state, representing a sudden change in physical properties. Subsequently, exothermic and endothermic peaks appeared at 658.9°C and 733.9°C, respectively, indicating that crystallization had occurred in the glass material. Notably, an endothermic peak was observed at 900°C, suggesting that a new crystallization process may have occurred at higher temperatures, possibly due to the combined effects of multiple elements. As shown in Figure b2), the second heating in Example 3 produced a peak at the glass transition temperature, and an exothermic peak appeared at 894.7°C, indicating that the second heating likely induced another crystallization process. The occurrence of multiple crystallization processes is beneficial to the interaction between the glass phase and the crystalline phase, which has a positive effect on the adhesion of Yaotou black porcelain.

[0027] The glass powder is thoroughly mixed with ball milling agents, colloids, and deionized water to obtain a glass adhesive. This adhesive is then evenly applied to the cracks in the Yaotou black porcelain and sintered above the crystallization temperature of the glass powder. Through the synergistic effect of the glass and crystalline phases, adhesion at the cracks in the Yaotou black porcelain is promoted, and the repaired porcelain gains a certain degree of mechanical strength.

Claims

1. A glass adhesive for repairing Yaotou black porcelain, characterized in that, It comprises the following components by weight percentage: 40%~55% quartz powder; 5%~21% calcined alumina; 0.5~16% B2O3; 0.5~20% CaO 4%~12% MgO; 1%~10% K2O; 1%~3% ZrO2; 0~16% Li2O; 0.2~1.6% TiO2; 0%~15% P2O5; 16% Na2CO3.

2. A method for preparing a glass adhesive for repairing Yaotou black porcelain, characterized in that, Includes the following steps: Step 1: According to the mass percentage, add 40%~55% quartz powder, 5%~21% calcined alumina, 0.5~16% B2O3, 0.5~20% CaO, 4%~12% MgO, 1%~10% K2O, 1%~3% ZrO2, 0~16% Li2O, 0.2~1.6% TiO2, and 0%~15% P2O5, and additionally add 16% Na2CO3. Pour the mixture into a nylon ball mill jar for wet ball milling, dry it, and then sieve it. The raw material for B2O3 is boric acid, the raw material for CaO is CaCO3, the raw material for K2O is K2CO3, the raw material for Li2O is Li2CO3, and the raw material for P2O5 is ammonium dihydrogen phosphate. Step 2: Transfer the mixed raw materials to a quartz crucible inside a glass furnace that has been preheated to 1000-1100℃. Hold the temperature for the first time, then raise the temperature of the glass furnace to 1450℃ at a heating rate of 2~3℃ / min, and hold the temperature again to fully melt the mixed powder and obtain high-temperature molten material A. Step 3: Quickly open the glass furnace, pour the high-temperature molten material A into the liquid quenching medium and stir constantly to prevent sticking and cool down quickly. Collect the irregular glass shards after cooling. Step 4: Ultrasonically clean and dry the collected irregular glass fragments, then transfer the glass fragments into a mortar and grind them into glass powder B. Step 5: PVA, anhydrous ethanol and deionized water are poured into a water bath and stirred until they are evenly mixed. The water bath is then heated to 90°C and kept at that temperature for 12 hours to obtain colloidal C. Step 6: Pour the ball stone, glass powder B, colloid C, and deionized water into a nylon ball mill jar and ball mill for 24 hours to obtain mixed colloid D, which is the glass adhesive.

3. The preparation method of the glass adhesive for repairing Yaotou black porcelain according to claim 1, characterized in that, In step 1, the liquid medium for wet ball milling can be distilled water or anhydrous ethanol, and the mass ratio of raw material, liquid medium and ball milling is 1:6:

2.

4. The preparation method of the glass adhesive for repairing Yaotou black porcelain according to claim 1, characterized in that, The initial heat preservation time in step 2 is 10-15 minutes; the second heat preservation time is 40-55 minutes.

5. The preparation method of the glass adhesive for repairing Yaotou black porcelain according to claim 1, characterized in that, The liquid quenching medium in step 3 is distilled water at a temperature of 10~20℃.

6. The preparation method of the glass adhesive for repairing Yaotou black porcelain according to claim 1, characterized in that, The liquid medium for wet ball milling in step 4 is distilled water, and the mass ratio of raw material, distilled water and ball is 1:3:1, and the diameter of the ball is less than 3 mm. The sieves used in steps 1 and 4 are both 200 mesh.

7. The preparation method of the glass adhesive for repairing Yaotou black porcelain according to claim 1, characterized in that, In step 5, during the heating and heat preservation stage, a water bath with magnetic stirring function must be used to stir the colloid, and the opening of the water bath must be sealed with plastic wrap to prevent excessive evaporation of moisture.

8. The preparation method of the glass adhesive for repairing Yaotou black porcelain according to claim 1, characterized in that, In step 6, the ratio of spherical particles, glass powder, colloid, and deionized water is 3:2:0.6:

3.

9. A glass adhesive for repairing Yaotou black porcelain according to claim 1, characterized in that, Glass bonding is used to repair Yaotou black porcelain.

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